Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02240973 1998-06-18
IMPROVED ANTIOXIDANT SYSTEM
FOR LUBRICATION BASE OILS
TECHNICAL FIELD
This invention relates to an antioxidant system which exhibits excellent
nitrite elastomer
seal compatibility and its use in fully formulated lubricants. More
specifically, this invention
relates to antioxidant compositions comprising (A) at least one secondary
diarylamine, (B) at
least one sulfurized olefin and/or sulfurized hindered phenol, and (C) at
least one oil soluble
molybdenum compound.
BACKGROUND
Lubricating oils as used in the internal combustion engines of automobiles and
trucks are
subjected to a demanding environment during use. The environment results in
the oil suffering
oxidation which is catalyzed by the presence of impurities in the oil and is
promoted by the
elevated temperatures of the oil during use. The oxidation of lubrication oils
during use is
usually controlled to some extent by the use of antioxidant additives which
may extend the
useful life of the oil, particularly by reducing or preventing unacceptable
viscosity increases.
It has now been discovered that a combination of (A) secondary diarylamine(s),
(B)
sulfurized olefins) and/or sulfurized hindered phenol(s), and (C) oil soluble
molybdenum
compounds gives a highly effective antioxidant system.
U.S. patent 5,605,880 discloses alkylated diphenylamines and phenyl-alpha-
naphthyl
amines in combination with oxymolybdenum sulfide dithiocarbamates and
oxymolybdenum
sulfide organophosphorodithioates in lubricant compositions. However, these
references do not
teach the use of sulfurized olefins or sulfurized hindered phenols.
WO 95/07963 discloses mixtures of sulfur containing molybdenum compounds and
CA 02240973 1998-06-18
alkylated diphenylamines. The reference mentions that other antioxidants, such
as sulfurized
olefins or sulfurized hindered phenols, may be present, however, the reference
does not
specifically teach the use of a three component antioxidant system or
recognize that the three
component systems exhibit significantly more effective antioxidant systems
than the two
component compositions of the reference.
SUMMARY OF THE INVENTION
An objective of this invention is to impart a very high level of oxidation
protection and
viscosity control, without hardening nitrite elastomer seals, to fully
formulated lubricant
compositions containing low levels of ZDDP derived phosphorus, typically less
than 850 ppm of
phosphorus, using hydrocracked and/or hydroisomerized mineral base oils, by
incorporating into
said lubricant compositions an antioxidant composition comprising (A)
secondary diarylamines,
(B) sulfurized olefins andlor sulfurized hindered phenols, and (C) at least
one oil soluble
molybdenum compound. This three component antioxidant system
provides antioxidant protection for the above mentioned base oils that is
superior to the
protection obtained with combinations of any two of these components.
In one aspect, the invention is directed to lubricating cil compositions
comprising a base
oil and an antioxidant composition comprising (A) secondary diarylamines, (B)
sulfurized
olefins and/or sulfurized hindered phenols, and (C) at least one oil soluble
molybdenum
compound.
In another aspect, the invention is directed to a method for improving the
antioxidancy
and nitrite elastomer seal compatibility of a lubricant by incorporating in
the lubricant an
antioxidant composition comprising (A) secondary diarylamines, (B) sulfurized
olefins and/or
sulfurized hindered phenols, and (C) at least one oil soluble molybdenum
compound.
In yet another aspect, the invention is directed to a lubrication oil
concentrate comprising
CA 02240973 1998-06-18
a solvent and a combination of (A) secondary diarylamines, (I3) sulfurized
olefins and/or
sulfurized hindered phenols, and (C) at least one oil soluble molybdenum
compound.
DETAILED DESCRIPTION OF THE INVENTION
Component (A) - Secondary diarylamines
The secondary diarylamines used in this invention should be soluble in the
formulated oil
package or package conccntrate. Preferably the secondary diarylamine has the
general formula:
R,-NH-R2, wherein R, and Rz each independently represents a substituted or
unsubstituted aryl
group having from 6 to 30 carbon atoms. Illustrative substituents for the aryl
include alkyl
groups having from 1 to 20 carbon atoms, alkylaryl groups, hydroxy, carboxy
and nitro groups.
The aryl is preferably substituted or unsubstituted phenyl or naphthyl,
particularly wherein one
or both of the aryl groups are substituted with an alkyl. It is preferred that
both aryl groups be
alkyl substituted.
Examples of secondary diarylamines which can be used in the present invention
include
diphenylamine, alkylated diphenylamines, 3-hydroxydiphenylamine, N-phenyl-1,2-
phenylenediamine, N-phenyl-1,4-phenylenediamine, butyldiphenylamine,
di:butyldiphenylamine,
octyldiphenylamine, dioctyldiphenylamine, nonyldiphenylamine,
dinonyldiphenylamine, phenyl-
alpha-naphthylamine, phenyl-beta-naphthylamine, heptyldiphenylamine,
diheptyldiphenylamine,
methylstyryldiphenylamine, mixed butyl/octyl alkylated diphenylamines, mixed
butyl/styryl
alkylated diphenylamines, mixed ethyl/nonyl alkylated diphenylamines, mixed
octyUstyryl
alkylated diphenylamines, mixed ethyl/methylstyryl alkylated diphenylamines,
octyl alkylated
phenyl-alpha-naphthylamine and combinations of these of varying degrees of
purity that are
commonly used in the petroleum industry.
Examples of commercial secondary diarylamines include Irganox~ L06 and
Irganox~ L57
from Ciba-Geigy Corporation; Naugalube~ AMS, Naugalube~ 438, Naugalube~ 438R,
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Naugalube~ 438L, Naugalube~ 500, Naugalube~ 640, Naugalube~ 680, and Naugard~
PANA
from Uniroyal Chemical Company; Goodrite~ 3123, Goodrite~
3190X36, Goodritem 3127, Goodrite~ 3128, Goodrite~ 3185X1, Goodrite~ 3190X29,
Goodrite~
3190X40, and Goodrite~ 3191 from BF Goodrich Specialty Chemicals; Vanlube~
DND,
Vanlube~ NA, Vanlube~ PNA, Vanlube~ SL, Vanlube~ SLHP, Vanlube~ SS, Vanlube~
81,
Vanlube~ 848, and Vanlube~ 849 from R. T. Vanderbilt Company, Inc.
It is preferred that the nitrogen content of the secondary diarylamines be
between about 2
wt% and about 12 wt% of the neat additive concentrate. The concentration of
the secondary
diarylamine in the formulated lubricant oil can vary depending upon the
customers requirements
and applications, and the desired level of antioxidant protection required for
the specific
formulated oil. Typically the secondary diarylamines are present in the
formulated oil in an
amount of about 0.05 wt% to about 0.5 wt%, preferably from about 0.1 wt% to
about 0.4 wt%.
Component (B) - Sulfurized olefins and/or sulfurized hindered phenols
The sulfurized olefins useful in the present invention can be prepared by a
number of
known methods. They are characterized by the type of olefin used in their
production and their
final sulfur content. High molecular weight olefins, i.e., those olefins
having an average
molecular weight of 168 to 351 g/mole, are preferred. Examples of olefins that
may be used
include alpha-olefins, isomerized alpha-olefins, branched olefins, cyclic
olefins, and
combinations of these.
Suitable alpha-olefins include any C4-C25 alpha-olefins. Alpha-olefins may be
isomerized
before the sulfurization reaction or during the sulfurization reaction.
Structural and/or
conformational isomers of the alpha olefin that contain internal double bonds
and/or branching
may also be used. For example, isobutylene is the branched olefin counterpart
of the alpha-
olefin 1-butene.
4
CA 02240973 1998-06-18
Sulfur sources that may be used in the sulfurization reaction include:
elemental sulfur,
sulfur monochloride, sul fur dichloride, sodium sulfide, sodium polysulfide,
and mixtures of these
added together or at different stages of the sulfurization proceas.
Unsaturated fatty acids and oils, because of their unsaturation, may also be
sulfurized and
used in this invention. Examples of fatty acids that may be used include
lauroleic acid,
myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid,
linoleic acid, linolenic
acid, gadoleic acid, arachidonic acid, erucic acid, and mixtures of these.
Examples of oils or fats
that may be used include corn oil, cottonseed oil, grapeseed oil, olive oil,
palm oil, peanut oil,
rapeseed oil, safflower seed oil, sesame seed oil, soyabean oil, sunflower
seed oil, and
combinations of these.
The concentration of sulfurized olefin in the formulated lubricant oil can
vary depending
upon the customers requirement and applications, and the desired level of
antioxidant protection
required for the specific formulated oil. An important criteria for selecting
the concentration of
the sulfurized olefin used in the formulated oil is the sulfur concentration
of the sulfurized
olefin itself. The sulfurized olefin should deliver between 0.05 wt% and 0.30
wt% of sulfur to
the finished lubricant formulation. For example, a sulfurized olefin
containing 20 wt% sulfur
content should be used at levels between 0.25 wt% and 1.5 wt% to deliver
between 0.05 wt%
and 0.30 wt% sulfur to the finished oil. A sulfurized olefin containing 10 wt%
sulfur content
should be used between 0.5 wt% and 3.0 wt% to deliver between 0.05 wt% and
0.30 wt% sulfur
to the finished oil.
Examples of commercial sulfurized olefins which may be used in the present
invention
include HiTEC~ 7084 which contains approximately 20 wt% sulfur content, HiTEC~
7188 which
contains approximately 12 wt% sulfur content, HiTEC~ 312 which contains
approximately 47.5
wt% sulfur content, and HiTEC~ 3l3 which contains approximately 47.5 wt%
sulfur content, all
from Ethyl Corporation, and Additin~ RC 2540-A which contains approximately 38
wt% sulfur
CA 02240973 1998-06-18
content, from Rhein Chemie Corporation. Commercially available sulfurized
fatty oils, or
mixtures of sulfurized fatty oils and olefins, that may be used in the present
invention include
Additin~ R 44l0 which contains approximately 9.5 wt% sulfur content, Additin~
R 4412-F
which contains approximately 12.5 wt% sulfur content, Additin~ R 44l7 which
contains
approximately 17.5 wt% sulfur content, Additin~ RC 2515 which contains
approximately 15
wt% sulfur content, Additin~ RC 2526 which contains approximately 26 wt%
sulfur content,
Additin~ RC 2810-A which contains approximately 10 wt% sulfur content,
Additin~ RC 2814-A
which contains approximately 14 wt% sulfur content, and Additin~ RC 2818-A
which contains
approximately 16 wt% sulfur content, all from Rhein Chemie Corporation. It is
preferred that
the sulfurized olefin and/or fatty oil be a liquid of low corrosi~rity and low
active sulfur content
as determined by ASTM-D 1662.
The sulfurized hindered phenols suitable for use in the present invention can
be prepared
by a number of known methods. They are characterized by the type of hindered
phenols used in
their production and their final sulfur content. Hindered tert-butylphenols
are preferred. The
sulfurized hindered phenols may be chlorine-free, being prepared from chlorine-
free sulfur
sources such as elemental sulfur, sodium sulfide, or sodium polysulfide, or
they may contain
chlorine, being prepared from chlorinated sulfur sources such as sulfur
monochloride and sulfur
dichloride. Preferred sulfurized hindered phenols include those of the
following general
structure.
CA 02240973 1999-03-17
HO
x
[ S]
R,
Zz
wherein R is an alkyl group, R, is selected from the group consisting of alkyl
groups and
hydrogen, one of Z or Z, is OH with the other being hydrogen, one of Z~ or Z3
is OH with the
other being hydrogen, x is in the range of from 1 to 6, and y is in the range
of from 0 to 2.
Suitable chlorine-free, sulfurized hindered phenols may be prepared by the
methods
taught in U.S. Patent No. 3,929,654 or may be obtained by (a) preparing a
mixture of (i) at least
one chlorine-free hindered phenol, (ii) a chlorine-free sulfur source, and
(iii) at least one alkali
metal hydroxide promoter, in a polar solvent, and (b) causing components (i),
(ii) and
(iii) to react for sufficient time and at a sufficient temperature so as to
form at least one
chlorine-free sulfurized hindered phenol, as taught in co-pending Canadian
Application
No. 2,229,72l and EPO publication No. EP 0 811 631 (published December 10,
l997).
Suitable sulfurized hindered phenol products prepared from a chlorinated
sulfur
source include those products taught in U.S. Patent Nos. 3,250,712 and
4,946,610.
Examples of sulfurized hindered phenols that may be used in this invention
include 4,4'-
thiobis(2,6-di-t-butylphenol), 4,4'-dithiobis(2,6-di-t-butylphenol), 4,4'-
thiobis(2-t-butyl-6-
methylphenol), 4,4'-dithiobis(2-t-butyl-6-methylphenol), 4.4'-thiobis(2-t-
butyl-~-methylphenol),
7
CA 02240973 1999-02-09
and mixtures of these.
It is preferred that the sulfurized hindered phenols be a substantially liquid
product. As
used herein, substantially liquid refers to compositions that are chiefly
liquid. In this regard,
aged samples of the sulfurized hindered phenols may form a slight amount of
crystallization,
generally around the sides of the container where product comes in contact
with air and the glass
container surface. It is further preferred that the sulfurized hindered
phenols be chlorine-free, of
low corrosivity and having a high content of monosulfide as described in co-
pending
Canadian Application No. 2,229,721 and EPO publication EP 0 811 631. It is
also
preferred that the sulfur content of the sulfurized hindered phenol be in the
range of
4.0 wt% to l2.0 wt% of the additive concentrate.
The concentration of the sulfurized hindered phenol in the formulated
lubrication oil can
vary depending upon the customers requirements and applications, as well as
the desired level of
antioxidant protection required for the specific formulated oil. A preferred
use range is between
0.3 wt% and 1.5 wt% in the finished formulated oil.
Mixtures of sulfurized olefins and sulfurized hindered phenols may also be
used.
Component (C) - Oil soluble molybdenum compounds
Any oil soluble molybdenum compounds may be used in this invention. A critical
requirement is the quantity of molybdenum delivered to the finished formulated
oil. The
quantity will vary depending upon the customers requirements and applications,
and the desired
level of antioxidant protection required for the specific formulated oil.
Preferred concentrations
of molybdenum are between 60 ppm and 1000 ppm in the finished formulated oil.
For example,
an oil soluble molybdenum compound containing 8.0 wt% molybdenum content
should be used
between 0.08 wt% and 1.25 wt% to deliver between 64 ppm and 1000 ppm
molybdenum to the
finished oil.
8
CA 02240973 1999-02-09
Examples of some oil soluble molybdenum compounds that may be used in this
invention
include molybdenum dithiocarbamates, oxymolybdenum sulfide dithiocarbamates,
molybdenum
dithioxanthogenates, oxymolybdenum sulfide dithioxanthogenates, molybdenum
organophosphorodithioatcs, oxymolybdenum sulfide organophosphorodithioates,
molybdenum
carboxylates, molybdenum amine complexes, molybdenum alcohol complexes,
molybdenum
amide complexes, mixed molybdenum amine/alcohol/amide complexes, and
combinations of
these. Examples of commercially available oil soluble molybdenum compounds
that may be
used in the present invention include molybdenum octoate, which contains
approximately 8.5 wt
molybdenum content, available from the Shepherd Chemical Company; molybdenum
HEX-
CEM, which contains approximately 15.0 wt% molybdenum content, available from
the OM
Group; Molyvan~ 855, which contains approximately 8.0 wt% molybdenum content,
Molyvan~
807, which contains approximately 4.9 wt% molybdenum content, and Molyvan~
822, which
contains approximately 4.9 wt% molybdenum content, all available from R. T.
Vanderbilt
Company, Inc.; SAKURA-LUBE~ l00, which contains approximately 4.1 wt%
molybdenum
content, SAKURA-LUBEm 1 S5, which contains approximately 4.5 wt% molybdenum
content,
SAKURA-LUBE~ 600, which contains approximately 27.5 wt% molybdenum content,
and
SAKURA-LUBE~ 700, which contains approximately 4.5 wt% molybdenum content, a11
available from Asahi Denka Kogyo K. K.
Phosphorus-free molybdenum compounds are preferred for use in crankcase oil
formulations due to the trend to reduce the phosphorus content of motor oils
to attain improved
automobile catalyst compatibility. Further, it is important to note that the
use of sulfurized
olefins and sulfurized hindered phenols in finished oils can be limited due to
the presence of
active sulfur in these additives. Active sulfur can be defined in a number of
ways. One test
method that determines the amount of active sulfur in an additive is ASTM-D
1662. The
presence of active sulfur can also be determined by lubricant bench tests
sensitive to the presence
* Trade-mark
CA 02240973 1998-06-18
of active sulfur. For example, ASTM-D 130 shows high levels of copper
corrosion for lubricants
containing substantial amounts of active sulfur. Also, the Allison C-4 Nitrite
Seal Test shows
high levels of nitrile seal hardening for lubricants containing substantial
amounts of active sulfur.
Lubricants with high levels of active sulfur are undesirable because of these
seal compatibility
and corrosion concerns. However, these same additives are also very effective
high temperature
antioxidants. There is a need for a formulation method that would allow the
use of antioxidants
containing active sulfur but not cause excessive copper corrosion or nitrite
seal incompatibility.
The use of oil soluble sulfur-free molybdenum compounds, in combination with
secondary
diarylamines and the sulfurized olefins and/or sulfurized hindered phenols
described above,
provides both superior antioxidant properties and excellent nitrite seal
compatibility required for
proper formulation of lubricant oils.
Typically, the antioxidant composition is added to the oil in the form of a
package
concentrate. The amount of product in the concentrates generally varies from
about 5 wt% to 75
wt%, preferably from about 5 wt% to about 50 wt%. The concentrates may also
contain other
additives such as dispersants, detergents, anti-wear agents, supplemental
antioxidants, viscosity
index improvers, pour point depressants, corrosion inhibitors, rust
inhibitors, foam inhibitors, and friction modifiers.
The dispersants typically are nonmetallic additives containing nitrogen or
oxygen polar
groups attached to a high molecular weight hydrocarbon chain. The hydrocarbon
chain provides
solubility in the hydrocarbon base stocks. The dispersants function to keep
oil degradation
products suspended in the oil. Examples of suitable dispersants include
polymethacrylates and
styrene malefic ester copolymers, substituted succinimides, polyamine
succinimides, polyhydroxy
succinic esters, substituted Mannich bases, and substituted triazoles.
Generally, the dispersant, if
used, will be present in the finished oil in an amount of about 3 wt% to about
10 wt%.
The detergents typically are metallic additives containing metal ions and
polar groups,
CA 02240973 1998-06-18
such as sulfonates or carboxylates, with aliphatic, cycloaliphatic, or
alkylaromatic chains. The
detergents function by lifting deposits from the various surfaces of the
engine. Suitable
detergents include neutral and overbased alkali and alkaline earth metal
sulfonates, neutral and
overbased alkali and alkaline earth metal phenates, sulfurized phenates, and
overbased alkaline
earth salicylates. Generally, the detergent, if used, will be present in the
finished oil in an
amount of about 1 wt% to about 5 wt%.
Anti-wear additives are generally incorporated into lubricant formulations. A
commonly
used anti-wear agent, especially for use in formulated crankcase oils, is zinc
dihydrocarbyl
dithiophosphate (ZDDP). These additives function by reacting with the metal
surface to form a
new surface active compound which itself is deformed and thes protects the
original engine
surface. The ZDDP's are responsible for delivering phosphorus to the finished
formulated
lubricating oils. In crankcase applications, today's passenger car SJ oils
have a maximum limit
of 1000 ppm phosphorus that is allowed in the finished oil. The presence of
phosphorus in
finished formulated crankcase oils is believed to increase automotive
emissions and thus
contribute to pollution. It is therefore desirable to reduce the level of
phosphorus, and therefore
the level of ZDDP, in finished oils. However, the ZDDP's are very powerful
antioxidants.
Removal of ZDDP from the finished oils places severe demands on the other
antioxidants
present in the oil. The three component antioxidant system of this invention
is highly effective at
reduced phosphorus level, e.g., between 500 ppm and 850 ppm, without sacrifice
of antioxidant
performance.
Supplemental antioxidants, i.e., antioxidants in addition to the three
component
antioxidant system of the present invention, may be used in oils that are less
oxidatively stable or
in oils that are subjected to unusually severe conditions. The antioxidant
protection provided by
the present three component system is not likely to require additional
antioxidants. However,
cost factors and engine oil compatibility issues may require the use of other
antioxidants.
11
CA 02240973 1998-06-18
Suitable supplemental antioxidants include hindered phenols, hindered
bisphenols, sulfurized
alkylphenols, dialkyl dithiocarbamates, phenothiazines, and oil soluble copper
compounds.
The optional viscosity index improver (VII) component of this invention may be
selected
from any of the known VIIs. The function of the VII is to reduce the rate of
change of viscosity
with temperature, i.e., they cause minimal increase in engine oil viscosity at
low temperatures
but considerable increase at high temperatures. Examples of suitable VIIs
include
polyisobutylenes, polymethacrylates, ethylene/propylene copolymers,
functionalized
ethylene/propylene copolymers, polyacrylates, styrene malefic ester
copolymers, and
hydrogenated styrene/butadiene copolymers.
The base oils used in forming the lubricating compositions of the present
invention are
characterized by the presence of a high level of saturates and a very low
level of sulfur,
compared to Group I base oils, and include base oils referred to in the
petroleum additive
industry as Group II and Group III base oils) A variety of methods may be used
to manufacture
these oils. The oils produced are generally referred to as severely
hydrotreated oils or
hydrocracked oils. They are prepared from conventional feedstocks using a
severe
hydrogenation step to reduce the aromatic, sulfur and nitrogen content,
followed by dewaxing,
hydrofinishing, extraction and/or distillation steps to produce the finished
base oil. The oils of
the present invention generally contain greater than or equal to 90%
saturates, less than or equal
to 0.03 weight percent sulfur and have a viscosity index of greater than or
equal to 80.
There are a number of recent trends in the petroleum additive industry that
may restrict
and/or limit the use of certain additives in formulated crankcase oils. The
key trends are the
move to lower phosphorus levels in oils, new fuel economy requirements, the
use of more highly
refined base oils, and the move to more severe engine and bench test
conditions for qualifying
oils. Such changes may show that certain currently used antioxidant additives
do not provide the
desired protection against oil oxidation. The three component antioxidant
system of the present
~2
CA 02240973 1999-02-09
invention provides a solution to this need. This invention also provides a
formulation method
that allows the use of sulfurized antioxidants that previously could not be
used because of
corrosion issues and nitrite seal compatibility issues.
EXAMPLES
Example 1
A series of passenger car motor oils were blended as defined in Table 1. The
oils were
formulated using polymeric dispersants, sulfonate detergents, ZDDP, an anti-
foam agent, a
viscosity index improver, a pour point depressant and a diluent process oil to
prepare SAE grade
SW-30 motor oils. The additive antioxidants and base oils used are defined in
Table 1. These
oils were evaluated in the Sequence IIIE engine test following ASTM STP 315H
Part 1. The
IIIE test uses a 23l CID (3.8) liter Buick V-6 engine at high speed (3,000
rpm) and a very high
oil temperature of 149~C for 64 hours. This test is used to evaluate an engine
oil's ability to
minimize oxidation, thickening, sludge, varnish, deposits, and high
temperature wear.
Additive package concentrate #1 was blended to deliver approximately 900 ppm
of
ZDDP derived phosphorus to the finished oil and was formulated with an amount
of polymeric
dispersant sufficient for effective sludge control in the conventional
hydrofinished oils. Additive
package concentrate #2 was blended to deliver approximately 900 ppm of ZDDP
derived
phosphorus to the finished oil and was formulated with an amount of polymeric
dispersant
sufficient for sludge control in the ultra low sulfur hydrocracked oils.
Additive package
concentrate #3 was blended to deliver approximately 820 ppm of ZDDP derived
phosphorus to
the finished oil and was formulated with an amount of polymeric dispersant
sufficient for sludge
control in the ultra low sulfur hydrocracked oils.
The 100N and 240N hydrocracked base oils were obtained from Chevron Chemical
Company and typically contain less than 50 ppm sulfur, less than S ppm
nitrogen, between 95
* Trade-mark
13
CA 02240973 1998-06-18
and 99% saturates, and between 1 and 4% aromatics. The 100N and 325N
hydrofinished base
oils were obtained from Ashland Oil Company and contained 0.31 wt% and 0.88
wt% sulfur,
respectively, and are further characterized, relative to the hydrocracked
oils, by a higher nitrogen
content, a lower level of saturates, and a higher level of aromatics.
The sulfurized olefin used was a C,~~B sulfurized olefin containing
approximately 20 wt%
sulfur, commercially available as HiTEC~ 7084 sulfurized olefin from Ethyl
Corporation. The
molybdenum 2-ethylhexanoate used was molybdenum HEX-CEM, an oil soluble
molybdenum
compound containing approximately 15 wt% molybdenum obtained from The OM
Group. The
organo molybdenum complex is Molyvan~ 855, a sulfur and phosphorus free
molybdenum
compound available from R. T. Vanderbilt Company, Inc. The alkylated
diphenylamine is
Naugalube~ 680, an octyl/styryl alkylated diphenylamine available from
Uniroyal Chemical
Company, Inc.
14
CA 02240973 1998-06-18
'!'ABLE 1. Antioxidant evaluations in the Sequence IIIE
Oil Oil Oil Oil Oil Oil Oil
#1* #2* #3* #4* #5* #6 #7
Package Type
Additive Package Conc.17.71517.7l
# 1 5
Additive Package Conc. 16.150 l6.015
#2
Additive Package Conc. 15.50015.50015.500
#3
Antioxidant Type
Sulfurized Olefin 0.700 0.700 0.700
Molybdenum 2-ethylhexanoate0.085 0.085 0.150 0.085 0.112
Organo Molybdenum Complex 0.210
alkylated diphenylamine0.200 0.200 0.200 0.400 0.300 0.300 0.300
Base Oil Type
100N Iow S hydrocracked 77.00072.900 72.90072.90072.90072.900
240N low S hydrocracked 5.000 10.600 10.600l0.60010.60010.600
100N hydrofinished 76.000
325N hydrofinished 6.000
Analytical
Calculated P (ppm) 900 900 900 900 820 820 820
Calculated Mo (ppm) l28 l28 225 l28 0 l68 l68
Viscosity increase(%
change)
8 hours 16 11 -5 -~ -3 -3 -4
16 hours 23 18 -6 -5 -2 -3 -4
24 hours 25 22 -8 -4 1 0 -1
32 hours 26 16 16 -4 1 2 0
40 hours 45 54 73 17 -3 5 -2
48 hours 85 140 194 84 l46 6 -6
56 hours l59 422 672 216 522 6 9
64 hours (375 Max) 300 2541 2486 854 3576 -1 40
IIIE Results Limits
Hrs to 375% Vis Inc. 66.4 54.7 51 58 52.9 85.8 81
Min 64
AE Sludge Min 9.2 9.56 9.34 9.25 9.36 9.25 9.75 9.62
APS Varnish Min 8.9 9.38 9.1 8.78 8.9 8.6 9.33 9
ORL Deposit Min 3.5 4.8 3.59 2.54 3.54 2.88 4.46 3.76
AC Wear Max 30 6.5 7.6 10.4 l0.6 10.5 11.8 8.8
MC Wear Max 64 11 11 14 20 13 15 13
Oil Consumption, L 3.55 3.61 3.73 3.21 3.89 2.56 2.78
Max 5.1
Comparative Examples
CA 02240973 1998-06-18
The Sequence IIIE results in Table I show a variety of effects. ( 1 ) A two
component
antioxidant system composed of molybdenum and alkylated diphenylamines is
effective at
controlling viscosity and passing the IIIE in the high sulfur hydrofinished
oils (Oil # 1 ), but is
much less effective in the ultra low sulfur hydrocracked oils (Oils #2-4) even
when adjusting the
antioxidant treat levels in the low sulfur hydrocracked oils. (2) A two
component antioxidant
composed of sulfizrized olefin and alkylated diphenylamines (Oil #5) is
ineffective at controlling
viscosity and passing the IIIE in the low sulfur hydrocracked oils containing
low (820 ppm)
levels of phosphorus. (3) When a three component antioxidant system of the
present invention
(Oils #6 and 7) composed of sulfurized olefin, alkylated diphenylamine, and
molybdenum is
used in the ultra Iow sulfur hydrocracked oils a significant improvement in
the oils ability to
control viscosity and pass the IIIE is seen.
The results of Table 1 clearly demonstrate that for effective viscosity
control in ultra low
sulfur hydrocracked oils formulated with low levels of phosphorus, a three way
antioxidant
system composed of sulfurized olefin, alkylated diphenylamines, and oil
soluble molybdenum
gives far superior results compared to conventional two component (i.e.,
molybdenum with
diphenylamines or sulfurized olefins with diphenylamines) antioxidant systems.
Example 2
An SAE grade 5 W-30 passenger car motor oil was blended as set forth in Table
2. Oils
#8 and 9 were formulated using an additive package concentrate composed of
polymeric
dispersants, sulfonate detergents, zinc dialkyl dithiophosphate (ZDDP), an
antifoam agent, a
viscosity index improver, a pour point depressant, a diluent process oil, and
the antioxidants
listed in Table 2. The two oils were evaluated in the Sequence IIIE engine
test as described in
Example 1 using the following modification. Because of the very high level of
effectiveness
exhibited by the three component antioxidant system of the present invention
it was necessary to
16
CA 02240973 1999-02-09
run prolonged Sequence IIIE tests. The actual length of each IIIE test run is
indicated in the
viscosity results section of Table 2. These oils were blended to deliver
approximately 740 ppm
of ZDDP derived phosphorus to the finished oil and were formulated with an
amount of
polymeric dispersant sufficient for sludge control in the ultra low sulfur
hydrocracked oils. The
100N and 240N ultra low sulfur hydrocracked base oils used are the same as
defined in Example
1. The sulfurized hindered phenol was prepared in a manner analogous to that
described in
Example 2 of EPO publication No. EP 0 811 631, and contained 10.75
wt% sulfur. The molybdenum 2-ethylhexanoate used was molybdenum octoate, an
oil soluble
molybdenum compound containing approximately 8.5 wt% molybdenum, commercially
available from The Shepherd Chemical Company. The alkylated diphenylamine used
was
Naugalubem 680, an octyl/styryl diphenylamine available from Uniroyal Chemical
Company, Inc.
TABLE 2. Antioxidant evaluations in the Sequence IIIE
Oil #8 Oil #9
_
Antioxidant Type
Sulfurized Hindered t-butylphenol0.600 l.000
Molybdenum 2-ethylhexanoate 0.100 0.800
alkylated diphenylamine 0.300 0.300
Base Oil Type
100N-Low sulfur hydrocracked 74.000 73.186
base oil
240N-Low sulfur hydrocracked 8.000 7.912
base oil
Analytical
Calculated P (ppm) 740 732
Calculated Mo (ppm) 85 680
Viscosity Increase Date (%
change)
8 hours -4.2 -6
16 hours -0.9 -5.1
24 hours 4 -1.5
32 hours 7.8 2.2
40 hours 9.7 ~.S
48 hours 6.3 8.5
I7
CA 02240973 1998-06-18
56 hours 33.2 10.9
64 hours (Single test complete)I43.9 12.9
72 hours 543.9 16
80 hours TVTM* 17.5
88 hours TVTM* 19.2
96 hours 20.l
l04 hours 22.7
112 hours 27.5
120 hours 34.8
128 hours (Double test complete) 49.4
Too viscous to measure
The Sequence IIIE results in Table 2 demonstrate a variety of benefits of the
three
component antioxidant system of the present invention. When a three component
antioxidant
system of the present invention is used in the low sulfur hydrocracked oils a
significant
improvement in the oils ability to control viscosity in the IIIE is seen
(compare Oils #2-5 in
Example 1 and Oils #8 and 9 in Example 2). Even though the ZDDP derived
phosphorus levels
in Oils #8 and 9 (approximately 740 ppm) are lower than the those of Example 1
(900 and 820
ppm), thus producing an oil more sensitive to oxidation and viscosity
increase, a significantly
more stable oil is seen due to the three component antioxidant system of the
present invention.
Further, when the treat levels of the three way antioxidant system are
increased (compare
Oil #8 and Oil #9) even better IIIE viscosity results are obtained, i.e., Oil
#9 passes a double run
of the Sequence IIIE for the viscosity parameter with very little increase in
viscosity.
Example 3
A sulfurized hindered phenol, a sulfizrized olefin, an alkylated
diphenylamine, and an oil
soluble molybdenum compound were blended into an SAE grade SW-30 passenger car
motor oil
as set forth in Table 3. The oils were formulated using identical additive
package concentrates
18
CA 02240973 1999-02-09
comprising polymeric dispersants, sulfonate detergents, zinc dialkyl
dithiophosphate (ZDDP),
an antifoam agent) a viscosity index improver, a pour point depressant, and a
diluent process oil.
These oils were blended to deliver approximately 820 ppm of ZDDP derived
phosphorus to the
finished oil and were formulated with an amount of polymeric dispersant
sufficient for sludge
control in the ultra low sulfur hydrocracked oils. The 100N and 240N ultra low
sulfur
hydrocracked base oils are as defined in Example 1. The sulfurized hindered
phenol was
prepared in a manner analogous to that described in Example 2 of EPO
publication
EP 0 811 631 ) and contained 10.22 wt% sulfur. The molybdenum 2-
ethylhexanoate used was molybdenum octoate, an oil soluble molybdenum compound
containing
approximately 8.5 wt% molybdenum, commercially available from The Shepherd
Chemical
Company. The alkylated diphenylamine used was Naugalube~ 680, an octyl/styryl
diphenylamine available from Uniroyal Chemical Company, Inc. The sulfurized
olefin used was
HiTECm 7084 sulfurized olefin described in Example 1.
The oxidation stability of these oils was measured by pressurized differential
scanning
calorimetry (PDSC) as described by J. A. Walker and W. Tsang in
"Characterization of
Lubrication Oils by Differential Scanning Calorimetry", SAE Technical Paper
Series, 801383
(October 20-23, l980). Oil samples were treated with an iron naphthenate
catalyst (55 ppm Fe)
and approximately 2 milligrams were analyzed in an open aluminum hermetic pan.
The DSC
cell was pressurized with 400 psi of air containing approximately 5 5 ppm NO,
as an oxidation
catalyst. The following heating sequence was used: Ramp 20 ~C/min to l20 ~C,
Ramp 10 ~C/min
to 1 SO ~C, Ramp 2.5 ~C to 250 ~C, Isothermal for 1 minute. During the
temperature ramping
sequence an exothermic release of heat is observed. This exothermic release of
heat marks the
oxidation reaction. The temperature at which the exothermic release of heat is
observed is called
the oxidation onset temperature and is a measure of the oxidative stability of
the oil (i.e., the
higher the oxidation onset temperature the greater the oxidative stability of
the oil). All oils are
19
CA 02240973 1998-06-18
evaluated in triplicate and the results averaged, the results are set forth in
Table 3.
The onset temperature results in Table 3 clearly show the advantage of the
three way
antioxidant system to control oxidation in fully formulated passenger car
motor oils. Note that
for entries containing only one or two components of the three component
antioxidant system,
there is an analogous three component entry that achieves equivalent or better
results, i.e.,
equivalent or higher onset temperatures, with less additives. For example, oil
#15 can achieve an
onset temperature of 206.5 with the use of 0.9 wt% of an antioxidant system
derived from the
use of only two components (the diphenylamine represents one component and the
combination
of sulfurized olefin and sulfurized hindered phenol represents the second
component). Within
experimental error, oils # 17 and # 18 achieve the same onset temperature
with, respectively,
0.675 wt% and 0.75 wt% of antioxidants derived from the three way system. Oil
#20 achieves a
higher onset temperature using only 0a75 wt% of antioxidant derived from the
three way
system. This type of response is seen consistently when comparing oils
containing only one or
two components with oils containing all three components. What is also
important is that
combinations of sulfurized olefins and sulfurized hindered phenols may be used
to represent one
of the components in the three component system. Some of the most powerful
antioxidant
combinations are seen when sulfurized olefins and sulfurized hindered phenols
represent one
component, with the remaining two components being molybdenum and
diphenylamine (oils #22
through #26).
TABLE 3. Evaluation of Antioxidants by PDSC
Oil Alkylated Sulfurized% S fromSulfurizedOil soluble ppm Total
AntioxidantOnset
# diphenylamineOlefin SulfurizedHinderedMolybdenum Mo Used %
Temperature
% Olefin Phenol % ~C
%
10* 0.20 0.2 196.9
11 * 0.20 0.40 0.080 0.6 200.6
12* 0.20 0.80 0.l60 1 203.S
13* 0.20 0.60 0.8 20S.7
14* 0.20 0.1 SO 128 0.3S 202.0
1 S* 0.20 0.40 0.080 0.30 0.9 206.S
n
16* 0.20 0.80 0.160 0.60 1.6 2l0.8
0
17 0.20 0.40 0.080 0.07S 64 0.67S 206.2
18 0.20 0.40 0.080 0.1 S0 128 0.7S 206.3
19 0.20 0.80 0.160 0.1 SO 128 1.1 S 207.9
20 0.20 0.30 0.07S 64 O.S7S 207.8
21 0.20 0.60 0.1 SO l28 0.9S 210.8
22 0.20 4.40 0.080 0.30 0.07S 64 0.99S 210.3
23 0.20 0.40 0.080 0.60 0.07S 64 1.27S 212.3
24 0.20 0.40 0.080 0.30 0.l50 128 1.0S 2l1.9
2S 0.20 0.80 0.l60 0.30 0.07S 64 1.37S 212.l
26 0.20 0.80 0.160 0.60 0.1 S0 128 1.7S 21 S.9
Comparative examples
CA 02240973 1998-06-18
Example 4
The following example shows the benefit of using sulfur-free molybdenum
compounds
versus sulfurized molybdenum compounds in crankcase lubricants.
A series of heavy duty diesel engine oils were blended as defined in Table IV.
The oils
were formulated using polymeric dispersants, sulfonate and phenate detergents,
ZDDP, an anti-
foam agent, a viscosity index improver, a pour point depressant, antioxidants,
a diluent process
oil, and a base oil, to prepare molybdenum-free SAE grade 15 W-40 motor oils.
The finished oils
were then top treated with a variety of sulfur containing and sulfur-free
molybdenum compounds
to deliver approximately 500 ppm molybdenum to each blend. The molybdenum
compounds
used were as follows: Sakura-Lube~ l55, a sulfur containing molybdenum
dithiocarbamate
available from Asahi Denka Kogyo K. K.; Sakura-Lube~ 700, a sulfur-free
molybdenum amine
complex available from Asahi Denka Kogyo K. K.; Molyvan~ 807 and 822, sulfur
containing
molybdenum dithiocarbamates available from R. T. Vanderbilt Company, Inc.;
Molyvan~ 855, a
sulfur-free organomolybdenum compound available from R. T. Vanderbilt Company,
Inc.; and
Molybdenum Octoate, a sulfur-free molybdenum carboxylate available from The
Shepherd
Chemical Company. These oils were evaluated for nitrite elastomer
compatibility using the
Allison C-4 Nitrite Seal Test, method GM 6137-M, test J1, total immersion
conditions. The
tested nitrite elastomers were rated for hardness change. This parameter is
especially sensitive to
sulfurized additives in the finished oil. Active sulfur has the effect of
hardening these seals, i.e.,
show an increase in the hardness rating. The results are shown in Table 4.
Note that although a11
molybdenum compounds show an improvement relative to the molybdenum-free
reference, the
sulfur-free molybdenum compounds show the largest improvement. This is an
advantage of the
sulfur-free molybdenum compounds since it allow greater flexibility in the
level and type of
sulfurized antioxidants that can be used in combination with molybdenum and
diphenylamines.
22
CA 02240973 1999-02-09
Table 4 Nitrite Seal Evaluation of Molybdenum Compounds
Oil SAE 15W- Molybdenum Wt% Mo Diluentppm Mo Hardness
# 40 Oil Compound Compound Oil DeliveredChange
(wt%) (wt%) to (+S to
Oil -5)
27 98.2 None 0 1.8 0 +5
28 98.2 Molyvan~ 85S 0.63 l.18 500 0
29 98.2 Sakura-Lube~ 1.1 I 0.69 S00 +1
700
30 98.2 Molybdenum 0.S9 1.21 500 +1
Octoate
31 98.2 Molyvan~ 8Q7 l.02 0.78 500 +2
32 98.2 Molyvan~ 822 1.02 0.78 500 +2
33 98.2 Sakura-Lube~ 1.1I 0.69 S00 +2
15S I
Example 5
The following example shows how sulfur-free molybdenum compounds can be used
in
this invention to produce nitrite seal compatible lubricants.
A sulfurized hindered phenol, a sulfurized olefin, an alkylated diphenylamine,
and an oil
soluble molybdenum compound were blended into an SAE grade 5W-30 passenger car
motor oil
as shown in Table V. The oils were formulated using polymeric dispersants,
sulfonate
detergents, ZDDP, an anti-foam agent, a viscosity index improver, a pour point
depressant and a
diluent process oil. These oils were blended to deliver approximately 820 ppm,
of ZDDP
derived phosphorus to the finished oil and were formulated with an amount of
polymeric
dispersant sufficient for sludge control in the ultra low sulfur hydrocracked
oils. The 100N and
240N ultra low sulfur hydrocracked base oils used were those defined in
Example 1. The
sulfurized hindered phenol was prepared in a manner analogous to that
described in
copending Canadian Application No. 2, 229, 721, Example 1, and contained
approximately 6.6 wt% sulfur. The molybdenum compound used was Molyvan~ 855,
an oil soluble organomolybdenum complex of an organic amide containing
approximately 8.0 wt% molybdenum obtain from R.T. Vanderbilt Company, Inc. The
alkylated diphenylamine used was an octyl/styryl alkylated diphenylamine
23
CA 02240973 1998-06-18
available from The BFGoodrich Company, Inc. The sulfurized olefin used was
HiTEC~ 7084
sulfurized olefin, which is a C,6-08 sulfurized olefin containing
approximately 20 wt% sulfur
obtained from Ethyl Corporation. These oils were evaluated for nitrite
elastomer compatibility
using the Allison C-4 Nitrite Seal Test as defined in Example 4. The results
are shown in Table
~. Note that samples without molybdenum fail the nitrite seal test for
hardness rating while
samples containing molybdenum pass. This effect is important because it allows
one to use
higher levels of sulfurized olefins and sulfurized hindered phenols without
having nitrite seal
incompatibility.
Table 5 Nitrite Seal Evaluation
Oil DiphenylamineSulfurizedSulfurizedMolybdenum DiluentSAE 5 Hardness
# W-
(wt%) HinderedOlefin Compound Oil 30 Oil Change
Phenol (wt%) (wt%, ppm (wt%) (wt%) (+S to
-5)
(wt%) Mo)
34 0.3 0, 0 1.7 98 +6
0.3 0.7 0, 0 1 98 +6
36 0.3 0.7 1.0, 800 98 +1
37 0.3 0.7 0, 0 1 98 +7
38 0.3 0.7 1.0, 800 ~ 98 +1
Example 6
A sulfurized hindered phenol, an alkylated diphenylamine, and oil soluble
molybdenum
compounds were blended into an SAE grade 5 W-30 passenger car motor oil as
shown in Table 6.
The oils were formulated using polymeric dispersant, sulfonate detergents,
ZDDP, an anti-foam
agent, a viscosity index improver, a pour point depressant and a diluent
process oil. These oils
were blended to deliver approximately 700 ppm of ZDDP derived phosphorus to
the finished oil
and were formulated with an amount of polymeric dispersant sufficient for
sludge control in the
ultra low sulfur hydrocracked oils. The 100N ultra low sulfur hydrocracked
base oil used was
that defined in Example 1. The sulfurized hindered phenol used was prepared in
a manner
24
CA 02240973 1999-02-09
analogous to that described in copending Canadian Application No. 2,229,721,
Example 1, and contained 6. 6 wt % sulfur. The molybdenum compounds used were
as
follows: molybdenum octoate, a sulfur-free molybdenum compound containing
approximately 8.5 wt% molybdenum obtained from The Shepherd Chemical Company;
Sakura-Lube~ 700, a sulfur-free molybdenum amine complex available from Asahi
Denka
Kogyo K. K. ; Molyvan~ 822, a sulfur containing molybdenum dithiocarbamate
available
from R.T. Vanderbilt Company, Inc.; and Molyvan~855, a sulfur-free
organomolybdenum compound available from R.T. Vanderbilt Company, Inc. The
alkylated diphenylamine used was an octyl/styryl alkylated diphenylamine
available from
The BFGoodrich Chemical Company, Inc. The oxidation stability of these oils
was
measured by pressurized differential scanning calorimetry (PDSC) as defined in
Example 3. The results are shown in Table 6. A11 samples (Oil # 39-53)
contained
97.30 wt% base SW-30 Oil blend and an amount of process diluent oil sufficient
to make
100 wt % of the total composition including base oil blend, antioxidants) and
diluent oil.
Note that if any one or two components of this invention is absent (oil blends
40 through
49), an oil with poor oxidative stability is produced. This example
demonstrates the
importance of having all three components, the diarylamine, the sulfurized
hindered
phenol, and the oil soluble molybdenum compound, to produce an oil with a high
level of
oxidative stability (oil blends 50 through 53) as indicated by the desired
higher onset
temperatures.
CA 02240973 1998-06-18
Table 6 Evaluation of Antioxidants by PDSC
0i1 Alkylated Sulfurized Molybdenum Oil Soluble Onset
# DiphenylamineHindered Compound Molybdenum Temperature
(wt%) Phenol (wt%) (wt%, ppm ~C
Mo)
39* 177.7
40* 0.70 195.3
41 Molyvan~ 85S 0.63, 500 180.2
*
42* Molyvan~ 822 1.02, 500 186.4
43* 0.70 Mo Octoate 0.59, 500 196.7
44* 0.70 Molyvan~ 85S 0.63, 500 197.1
45* 0.70 Molyvanm 822 1.02, S00 201.2
46* 0.70 Sakura-Lube~ 1.11, 500 198.2
70G
47* 0.20 Molyvan~ 855 0.63, 500 198.5
48* 0.20 Molyvan~ 822 1.02, 500 201.2
49* 0.20 0.70 202.4
50 0.20 0.70 Mo Octoate 0.59, 500 209.5
51 0.20 0.70 Molyvan~ 855 0.63, 500 209.1
52 0.20 0.70 Molyvan~ 822 1.02, 500 212.6
53 0.20 0.70 Sakura-Lube~ 1.11, 500 210.0
700
Comparative Examples
This invention is susceptible to considerable variation in its practice.
Accordingly, this
invention is not limited to the specific exemplifications set forth
hereinabove. Rather, this
invention is within the spirit and scope of the appended claims, including the
equivalents thereof
available as a matter of law.
The patentee does not intend to dedicate any disclosed embodiments to the
public, and to
the extent any disclosed modifications or alterations may not literally fall
within the scope of the
claims, they are considered to be part of the invention under the doctrine of
equivalents.
26
